KR20220062582A - Polythiophene in organic solvent - Google Patents

Abstract

The present invention provides: i) at least one polythiophene comprising a monomer unit of formula Ia or Ib, wherein * denotes a bond to a neighboring monomeric unit, X,Z denotes O or S, and R ¹ - R ⁶ independently of each other represents a hydrogen atom or an organic residue R, with the proviso that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ represent the organic residue R; ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein said organic compound or salt thereof has a molecular weight of less than 1,000 g/mol; and iii) at least one organic solvent. The present invention also relates to a method for preparing a composition, a composition obtainable by such method, a layer structure, a method for producing a layer structure, a layer structure obtainable by such method, an electronic component and a method of using the composition according to the invention will be.
[Formula Ia] [Formula Ib]

Description

Polythiophene in organic solvent

The present invention relates to a composition comprising at least one polythiophene. The present invention also relates to a method for preparing a composition, a composition obtainable by this method, a layer structure, a method for producing a layer structure, a layer structure obtainable by this method, an electronic component and a composition according to the invention It's about how to use it.

Polythiophenes are widely used in nature as conductive polymers. In particular, poly(3,4-ethylenedioxythiophene) (PEDOT) has many industrial applications such as solid electrolyte capacitors, antistatic coatings, electroluminescent lamps, organic light emitting diodes, organic solar cells and many other applications. found in the fields For many or these applications, PEDOT is a polymer complex with polystyrene-sulfonic acid (also referred to as "PEDOT/PSS") as a counter-ion dispersed in water or a mixture of water and other solvents. used) as

Efforts have been made to supply PEDOT in aprotic solvents to expand the range of applications. WO-A-2012/059215 A1 discloses the use of block-copolymers as counter-ions which render dispersions soluble in organic, aprotic solvents. The solubility parameters of the block-copolymer govern and limit the solubility properties of the resulting PEDOT complex. So, when a solvent such as PGMEA or ethanol is added, the dispersion becomes unstable.

KR-A-100945056 describes the polymerization of 3,4-ethylenedioxythiophene in water in the presence of a surfactant. After that, the solvent is removed and replaced with an organic solvent. However, this re-dispersion process is expensive and undesirable.

McCullough et al . (" A Simple Method to Prepare Head - to - Tail Coupled, Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis "; Adv. Mater. 1999, 11, 250) is a regioregular air that can be dispersed in multiple solvents. The synthesis of regioregular copolymers is described. However, coupling via metal-organic compounds is expensive, and the resulting polymer exhibits only limited conductivity. Thus, their application is limited to hole-transport layers, where only conductivity through the layer is required.

It is an object of the present invention to overcome the disadvantages of the prior art associated with electrically conductive polymers based on thiophene-monomers, preferably 3,4-ethylenedioxythiophene-monomers.

In particular, it is an object of the present invention. It is to provide a composition comprising polythiophene, which is based on an organic solvent, preferably an organic aprotic solvent, and which can be dispersed in a wide range of solvents. The composition should also be characterized in that the conductive layer made of such composition is highly conductive and highly transparent. Moreover, the composition should be able to achieve low sheet resistance (sheet resistance) when blended with inert polymers such as polyacrylates. Moreover, the compositions should be characterized in that they can be easily diluted with organic solvents.

It is also an object of the present invention to provide a process which enables the preparation of such advantageous compositions with as few process steps as possible.

A contribution to at least partly solving at least one, preferably more than one, of the above objects is made by the independent claims. The dependent claims provide preferred embodiments which serve at least in part to solve at least one of the above objects.

A contribution to solving at least one of the objects according to the invention is made by embodiment 1 of a composition 1 comprising the following components:

i) at least one polythiophene, preferably at least one cationic polythiophene, comprising monomer units of the formula la or lb;

[Formula Ia] [Formula Ib]

here,

* indicates a bond to a neighboring monomer unit,

X, Z represents O or S,

R ¹ -R ⁶ independently of each other represent a hydrogen atom or an organic residue R,

provided that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ represent the organic residue R;

ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein said organic compound or salt thereof has a molecular weight of less than 1,000 g/mol, preferably less than 900 g/mol, more preferably 800 g less than /mol, even more preferably less than 700 g/mol, even more preferably less than 600 g/mol and even more preferably less than 500 g/mol; and

iii) at least one organic solvent.

Hereinafter, the present invention is described in more detail with reference to the drawings, test methods and non-limiting examples.
1 shows a structure in general form of a layer structure 100 according to the invention, for example an antistatic film. In the case of an antistatic film, on the substrate surface of the substrate 101 , often a PE, PP or PET layer, is an electrically conductive layer 102 made of the composition according to the invention.

Surprisingly, polythiophenes comprising monomer units of formula Ia or Ib as described above, for example 3,4-ethylenedioxythiophene and 3, wherein at least one of the hydrogen atoms of the ethylene group is replaced by an organic moiety R; The copolymer of the derivative of 4-ethylenedioxythiophene, as a counter-ion, has a molecular weight of less than 1,000 g/mol, and has a sulfonic acid group (-SO ₂ OH), a sulfuric acid group (-O-SO ₂ OH), and a phosphonic acid group. An organic compound, preferably containing one or two inorganic acid group(s), such as (-PO(OH) ₂ ), a phosphoric acid group (-O-PO(OH) ₂ ), or a salt of at least one of these groups Using monovalent sulfonic acid anions, it has been found that they can be dispersed in a variety of solvents. The organic moiety R is an alkyl group, in particular a linear or branched alkyl group having the formula -C _n H _2n+1 (where n is an integer in the range from 1 to 20), preferably n is in the range from 3 to 15 and more preferably 3 When the organic moiety R corresponds to a branched ether group, or an integer ranging from 10 to 10, the complex of this polythiophene and an organic compound bearing one or two inorganic acid group(s) as described above comprises a composition comprising: It is particularly advantageous as a dispersion, preferably as a dispersion, wherein these complexes are dispersed in a protic or aprotic solvent, and in large quantities a non-conductive binder, certain poly(meth)acrylates, (meth)acrylic resins, and Polysilicon can be added without unduly reducing the conductivity of such compositions.

In embodiment 2 of composition 1 according to the invention, composition 1 is designed according to embodiment 1 thereof, wherein said composition is in the form of a dispersion or solution (herein organic solvent iii), preferably in an aprotic solvent iii ), thus serving as dispersant or solvent), wherein polythiophenes i) and organic compounds ii) (preferably in the form of anions), preferably copolymers i) and organic compounds Compound ii) forms a complex, dispersed or dissolved, preferably uniformly dispersed or dissolved, in the organic solvent iii). Most preferably, the composition according to the present invention is a dispersion in which a complex of polythiophene i) and organic compound ii) is uniformly dispersed in an organic solvent iii). However, in the composition according to the invention, the conversion between "dispersion" and "solution" may be fluid depending on the actual properties of the polythiophene i), the organic compound ii) and the organic solvent iii).

In embodiment 3 of the composition 1 according to the invention, composition 1 is designed according to embodiment 2 thereof, wherein the polythiophene/organic compound complex i)/ii) is in each case based on the total weight of the dispersion , 30% or less, preferably 20% or less and more preferably 10% or less.

In embodiment 4 of the composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 3 thereof, wherein the organic moiety R bears no anionic groups. Preferably, the residue R does not bear any sulfonic acid groups or salts of such groups.

In embodiment 5 of the composition 1 according to the present invention, composition 1 is designed according to any one of embodiments 1 to 4 thereof, wherein the organic moiety R is the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group. is selected from

In embodiment 6 of the composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 5 thereof, wherein the polythiophene is a monomer unit of the formula Ia or Ib, wherein X and Z are O , preferably a homopolymer or copolymer comprising a monomer unit of formula (Ia), wherein X and Z represent O, among the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ 3 and one of the residues selected from the group consisting of R ⁵ and R ⁶ represents a hydrogen atom and the remaining residues represent an ether group having the formula IIa:

[Formula IIa]

-(CR ⁷ R ⁸ ) _n -OR ⁹

here,

R ⁷ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁷ is H;

R ⁸ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁸ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, and even more preferably a C ₂ - C ₂₀ -alkyl group.

In embodiment 7 of the composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 5 thereof, wherein the polythiophene is a monomer unit of the formula Ia or Ib, wherein X and Z are O , preferably a homopolymer or copolymer comprising monomer units of formula Ia, wherein X and Z represent O and at least two of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ . and 1 selected from the group consisting of R ⁵ and R ⁶ , preferably 3 selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ and R ⁵ and R ⁶ One of the residues represents a hydrogen atom, the other residues represent an alkyl group, preferably the remaining residues represent an alkyl group having the formula (IIb):

[Formula IIb]

-C _n H _2n+1

Here, n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15 and still more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group, wherein The ethyl group, n-butyl group and n-decyl group are particularly preferred, wherein the n-butyl group is most preferred.

Suitable examples of monomer units of formula Ia bearing a branched alkyl group or more than one alkyl group include compounds selected from the group consisting of compounds (A), (B), (C) and (D):

In embodiment 8 of the composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 5 thereof, wherein the polythiophene is a monomer unit of the formula Ia or Ib, wherein X and Z are O , preferably a homopolymer or copolymer comprising monomer units of the formula Ia, wherein X and Z represent O, three of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ and One of the residues selected from the group consisting of R ⁵ and R ⁶ represents a hydrogen atom, and the remaining residues represent a branched alkyl group or a branched ether group, preferably a branched ether group, wherein in the sense of the present invention "min A topographic ether group" is preferably an oxygen atom in which at least one of the two organic moieties bonded to the oxygen atom is a branched organic moiety, i.e. at least three carbon atoms or at least two carbon atoms and an ether group via a single bond. an ether group, which is an organic moiety containing at least one carbon atom bonded to More preferably, the remaining moieties represent a branched ether group having the formula (IIc):

[Formula IIc]

-(CR ¹⁰ R ¹¹ ) _n -OR ¹²

here,

R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹⁰ is H;

R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹¹ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain, even more preferably preferably an organic moiety having the formula IId:

[Formula IId]

-(CHR ¹³ ) _m -R ¹⁴

here,

m is 1, 2 or 3,

R ¹³ is H or a C ₁ -C ₁₂ alkyl group, preferably a C ₂ -C ₁₀ alkyl group, more preferably a C ₃ -C ₈ alkyl group, even more preferably a butyl group, provided that the structural unit -CHR ¹³ - only one of, R ¹³ is a C ₁ -C ₁₂ alkyl group;

R ¹⁴ is a C ₁ -C ₁₀ -alkyl group, preferably a C ₂ -C ₆ -alkyl group, or an aryl group.

In embodiment 9 of composition 1 according to the invention, composition 1 is designed according to embodiment 8 thereof, wherein the polythiophene comprises a monomer unit selected from the group consisting of compounds (E), (F) and (G). It is a homopolymer or copolymer comprising:

With respect to embodiments 8 and 9 of the composition 1 according to the invention, organic compounds having more than two inorganic acid groups and having a molecular weight of more than 1,000 g/mol, such as polystyrene sulfonic acid (PSS), are used as component ii) It may also be possible to use

In embodiment 10 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 9 thereof, wherein at least one polythiophene i) is of formula la, wherein X and Z represent O A copolymer of 3,4-ethylenedioxythiophene with at least one derivative of 3,4-ethylenedioxythiophene, wherein at least one organic solvent iii) is preferably an aprotic solvent iii). In this case, polythiophene i) is thus a public group of 3,4-ethylenedioxythiophene and a derivative of at least one 3,4-ethylenedioxythiophene in which at least one of the hydrogen atoms of the ethylene group is replaced by an organic moiety R it is a composite

In embodiment 11 of composition 1 according to the invention, composition 1 is designed according to embodiment 10 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula Ia':

[Formula Ia']

Here, R is preferably selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.

In embodiment 12 of the composition 1 according to the invention, composition 1 is designed according to embodiment 11 thereof, wherein the organic moiety R is an ether group.

In embodiment 13 of composition 1 according to the invention, composition 1 is designed according to embodiment 12, wherein the ether group has the formula IIa:

[Formula IIa]

-(CR ⁷ R ⁸ ) _n -OR ⁹

here,

R ⁷ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁷ is H;

R ⁸ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁸ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, even more preferably a C ₂ -C ₂₀ -alkyl group.

In embodiment 14 of the composition 1 according to the invention, composition 1 is designed according to embodiment 13 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula (III):

[Formula Ⅲ]

Here, R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, even more preferably a C ₅ - C ₂₀ -alkyl group.

In embodiment 15 of the composition 1 according to the invention, composition 1 is designed according to embodiment 14 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula IV:

[Formula IV]

Here, m is an integer ranging from 0 to 24, preferably from 1 to 19, more preferably from 4 to 14, and most preferably m is 9.

In embodiment 16 of the composition 1 according to the invention, composition 1 is designed according to embodiment 11 thereof, wherein the organic moiety R is an alkyl group.

In embodiment 17 of composition 1 according to the present invention, composition 1 is designed according to embodiment 16 thereof, wherein the alkyl group has the formula IIb:

[Formula IIb]

-C _n H _2n+1

Here, n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15 and still more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group, wherein The ethyl group, n-butyl group and n-decyl group are particularly preferred, wherein the n-butyl group is most preferred.

In embodiment 18 of composition 1 according to the invention, composition 1 is designed according to embodiment 17 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula V:

[Formula V]

Here, n is in the range of 0 to 19, preferably in the range of 1 to 14, and more preferably in the range of 2 to 9. It is particularly preferred that n is 2, 3 or 4, where n = 3 is most preferred.

In embodiment 19 of the composition 1 according to the invention, composition 1 is designed according to embodiment 11 thereof, wherein the organic moiety R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group It is preferably a branched ether group having the formula (IIc):

[Formula IIc]

-(CR ¹⁰ R ¹¹ ) _n -OR ¹²

here,

R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹⁰ is H;

R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹¹ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain, even more preferably preferably an organic moiety having the formula IId:

[Formula IId]

-(CHR ¹³ ) _m -R ¹⁴

here,

m is 1, 2 or 3,

R ¹³ is H or a C ₁ -C ₁₂ alkyl group, preferably a C ₂ -C ₁₀ alkyl group, more preferably a C ₃ -C ₈ alkyl group, even more preferably a butyl group, provided that the structural unit -CHR ¹³ - only one of, R ¹³ is a C ₁ -C ₁₂ alkyl group;

R ¹⁴ is a C ₁ -C ₁₀ -alkyl group, preferably a C ₂ -C ₆ -alkyl group, or an aryl group.

In embodiment 20 of composition 1 according to the present invention, composition 1 is designed according to embodiment 19 thereof, wherein the polythiophene comprises a monomer unit selected from the group consisting of compounds (E), (F) and (G). It is a homopolymer or copolymer comprising:

In embodiment 21 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 20 thereof, wherein copolymer i) is the total number of monomer units (ie 3,4-ethylene 5 to 95% in each case based on dioxythiophene-monomer units and monomer units based on derivatives of 3,4-ethylenedioxythiophene), based on derivatives of 3,4-ethylenedioxythiophene monomer units, preferably from 10 to 80% monomer units and more preferably from 20% to 60% monomer units.

In embodiment 22 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 21 thereof, wherein copolymer i) is the total number of monomer units (ie 3,4-ethylene (total number of dioxythiophene-monomer units and monomer units based on derivatives of 3,4-ethylenedioxythiophene), in each case based on derivatives of 3,4-ethylenedioxythiophene, at least 30 wt% , preferably at least 40 wt % and more preferably at least 70 wt % monomer units.

In embodiment 23 of composition 1 according to the invention, composition 1 is designed according to embodiment 8 thereof, wherein at least one polythiophene i) is a copolymer of the following components:

α) at least one derivative of 3,4-ethylenedioxythiophene having the formula Ia';

[Formula Ia']

wherein R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group having the formula IIc as defined above;

β) at least one derivative of 3,4-ethylenedioxythiophene having the formula la';

[Formula Ia']

wherein R is an alkyl group having the formula IIb as defined above, wherein the thiophene derivative is 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxine, 2- Propyl-2,3-dihydrothieno-[3,4-b]-1,4-dioxine, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4- selected from the group consisting of dioxin, 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, 2-decyl-2,3-dihydrothieno[3 Preference is given to ,4-b][1,4]dioxine, wherein 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxine (butyl-EDOT) is particularly preferred,

and optionally

γ) 3,4-ethylenedioxythiophene.

In embodiment 24 of composition 1 according to the invention, composition 1 is designed according to embodiment 23 thereof, wherein copolymer i) comprises each of the monomers α), β) and γ) based on the total amount of the monomers α), β) and γ) in the copolymer. In this case, 5 to 99 mol%, preferably 15 to 70 mol% and more preferably 30 to 50 mol% monomer units, based on monomer α), 5 to 95 mol%, preferably based on monomer β) 30 to 90 mol % and more preferably 50 to 70 mol % monomer units, and 0 to 50 mol %, preferably 0 to 35 mol % and more preferably 0 to 20 mol %, based on the monomer γ) monomer units, wherein the sum of the amounts of monomers α), β) and γ) is up to 100 mol %. According to a particularly preferred copolymer i), the copolymer does not comprise 3,4-ethylenedioxythiophene as comonomer.

In embodiment 25 of composition 1 according to the present invention, composition 1 is designed according to any one of embodiments 1 to 24 thereof, wherein the inorganic acid group is a sulfonic acid group (-SO ₂ OH), a sulfuric acid group (-O-SO ₂ OH), a phosphonic acid group (-PO(OH) ₂ ), or a phosphoric acid group (-O-PO(OH) ₂ ), preferably a sulfonic acid group (-SO ₂ OH).

In embodiment 26 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 25 thereof, wherein the organic compound ii) is an anionic surfactant.

In embodiment 27 of composition 1 according to the invention, composition 1 is designed according to embodiment 26 thereof, wherein the anionic surfactant is sulfonic acid (R-SO ₂ OH), an ester of sulfuric acid (RO-SO ₂ OH) ) or a salt of one of these esters, preferably sulfonic acid. In this context, it is particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (ie a compound having only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.

In embodiment 28 of composition 1 according to the invention, composition 1 is designed according to embodiment 27 thereof, wherein the anionic surfactant is dodecylbenzene sulfonic acid or a salt thereof. As used herein, the term “dodecyl sulfonic acid” also refers to, in addition to dodecylbenzene sulfonic acid, an alkylbenzene sulfonic acid further including an alkylbenzene sulfonic acid having an alkyl chain longer or shorter than the dodecyl-group. encompasses mixtures.

In embodiment 29 of the composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 28 thereof, wherein the weight ratio of polythiophene i) to organic compound ii) or salt thereof, preferably air The weight ratio of coalescing i) to organic compound ii) or salt thereof is in the range of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2 and more preferably in the range of 1:5 to 1:0.5. am.

In embodiment 30 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 29 thereof, wherein at least one organic solvent iii), preferably at least one aprotic solvent iii) ) has a boiling point (determined at a pressure of 1013 mbar) in the range from 50 to 300 °C, preferably in the range from 60 to 250 °C and more preferably in the range from 70 to 220 °C.

In embodiment 31 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 30 thereof, wherein at least one organic solvent is an aprotic solvent iii), more preferably a polar It is an aprotic solvent.

In embodiment 32 of composition 1 according to the invention, composition 1 is designed according to embodiment 31 thereof, wherein the dielectric constant of the polar aprotic solvent iii) is less than 20, preferably less than 10 and more preferably is less than 7.

In embodiment 33 of composition 1 according to the invention, composition 1 is designed according to embodiments 31 or 32 thereof, wherein the polar aprotic solvent iii) is less than 4 D, preferably less than 2 D and more preferably has a dipole moment of less than 1.5 D.

In embodiment 34 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 33 thereof, wherein the at least one organic solvent iii) comprises aromatic hydrocarbons, esters, ethers, alcohols and these is selected from the group consisting of mixtures of

In embodiment 35 of composition 1 according to the invention, composition 1 is designed according to embodiment 34 thereof, wherein the at least one organic solvent iii) comprises toluene, xylene, anisole, methyl benzoate, ethyl benzoate, Propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2- propylacetate, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or mixtures of one or two of these aprotic solvents with one or two additional solvents. In the case of mixtures of two or more organic solvents, it is particularly preferred that at least one of these solvents is an aprotic solvent iii).

In embodiment 36 of composition 1 according to the present invention, composition 1 is designed according to any one of embodiments 1 to 35 thereof, wherein the composition comprises:

i) 0.01 to 20 wt%, preferably 0.02 to 10 wt%, more preferably 0.1 to 5 wt% of a polymer;

ii) 0.01 to 15 wt%, preferably 0.02 to 10 wt%, more preferably 0.1 to 5 wt% of an organic compound;

iii) from 50 to 99.98 wt%, preferably from 70 to 99.86 wt%, more preferably from 85 to 99.3 wt% of a solvent or solvent mixture, preferably an aprotic solvent or solvent mixture;

iv) 0 to 15 wt %, preferably 0.1 to 10 wt %, and more preferably 0.5 to 5 wt % of additives other than components i) to iii),

wherein the sum of the total weights of components i) to iv) is up to 100 wt %.

In embodiment 37 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 36 thereof, wherein the composition comprises, as a further component iv) different from components i) to iii), a conductive oligomer or a polymer, preferably a non-conductive oligomeric or polymeric binder. A "non-conductive oligomeric or polymeric binder" in the meaning of the present invention is an electrical conductivity of less than 10 ^-6 S/cm, preferably less than 10 ^-8 S/cm and most preferably less than 10 ^-10 S/cm. A layer of oligomer or polymer having In contrast, the "conductive polymer" (polythiophene i) or polythiophene-copolymer i)) in the composition according to the invention in the sense of the present invention is at least 10 ^-6 S/cm, preferably at least 10 ⁻ A layer of polymer with an electrical conductivity of ⁵ S/cm and most preferably 10 ^-4 S/cm is preferred.

In embodiment 38 of composition 1 according to the present invention, composition 1 is designed according to embodiment 37 thereof, wherein the non-conductive polymeric binder is polyolefin, polyvinyl acetate, polycarbonate, poly(meth)acrylate, poly Vinyl butyral, poly(meth)acrylic acid amide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, selected from the group consisting of polysulfone, polysilicon, epoxy resin, styrene-acrylate, vinyl acetate/acrylate or ethylene/vinyl acetate copolymer, polyvinyl alcohol, a cellulose derivative or a mixture comprising at least two of these polymers, Here, poly(meth)acrylate and polysilicon are particularly preferred non-conductive polymeric binders. Also suitable non-conductive polymeric binders are polyfunctional (meth)acrylates, such as dipentaerythritol penta-/hexaacrylate.

In embodiment 39 of composition 1 according to the invention, composition 1 is designed according to embodiment 38 thereof, wherein the poly(meth)acrylate is poly(methyl acrylate), poly(methyl methacrylate), poly(methyl methacrylate) (ethyl acrylate), poly(ethyl methacrylate), poly(n-propyl acrylate), poly(n-propyl methacrylate), poly(isopropyl acrylate), poly(isopropyl methacrylate), poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(isobutyl acrylate), poly(isobutyl methacrylate), poly(tert-butyl acrylate), poly(tert-butyl acrylate) methacrylate), poly(2-ethylhexyl acrylate), poly(2-ethylhexyl methacrylate), poly(cyclohexyl acrylate), poly(cyclohexyl methacrylate), poly(phenyl acrylate), poly(phenyl methacrylate), poly(benzyl acrylate), poly(benzyl methacrylate) and copolymers of these polyacrylates or polymethacrylates.

In embodiment 40 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 37 to 39 thereof, wherein the composition comprises a non-conductive polymeric binder iv), preferably poly(meth)acrylate and/or polysilicon and polythiophene/organic compound complex i)/ii) in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

In embodiment 41 of the composition 1 according to the invention, the composition 1 is designed according to any one of embodiments 37 to 40 thereof, wherein the conductive layer made of the composition is at most 1 x 10 ¹⁰ Ohm/sq, preferably has a sheet resistance of at most 5×10 ⁹ Ohm/sq and more preferably at most 1×10 ⁸ Ohm/sq.

In embodiment 42 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 41 thereof, wherein the composition comprises, in each case based on the total weight of the composition, less than 2 wt%; preferably less than 1 wt % and most preferably less than 0.1 wt % water.

In embodiment 43 of composition 1 according to the invention, composition 1 is designed according to any one of embodiments 1 to 42 thereof, wherein the composition, in each case based on the total weight of the composition, is less than 30 ppm, preferably preferably less than 15 ppm and more preferably less than 5 ppm total metal content. Metals include, inter alia, sodium, potassium and iron. Most preferably, the composition has an iron content of less than 30 ppm, preferably less than 15 ppm and more preferably less than 5 ppm, in each case based on the total weight of the composition.

In embodiment 44 of the composition 1 according to the invention, the composition 1 is designed according to any one of embodiments 1 to 43 thereof, wherein the conductive layer made of the composition is greater than 1 S/cm, preferably 2 S/cm have a conductivity greater than cm and most preferably greater than 5 S/cm.

A contribution to solving one or more of the objects according to the invention is also made by embodiment 1 of method 1 for preparing a composition, preferably a dispersion, said method comprising the steps of:

I) providing a reaction mixture comprising

i) a thiophene monomer of formula (VIa) or (VIb);

[Formula VIa] [Formula VIb]

here,

X, Z represents O or S,

R ¹ -R ⁶ independently of each other represent a hydrogen atom or an organic residue R,

provided that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ represent the organic residue R;

ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein said organic compound or salt thereof has a molecular weight of less than 1,000 g/mol, preferably less than 900 g/mol, more preferably 800 g less than /mol, even more preferably less than 700 g/mol, even more preferably less than 600 g/mol and even more preferably less than 500 g/mol;

iii) at least one organic solvent, and

iv) at least one oxidizing agent, preferably at least one organic, metal-free oxidizing agent, more preferably at least one organic peroxide;

II) for the formation of polythiophenes, preferably for the formation of cationic polythiophenes, more preferably for the formation of complexes of polythiophenes with organic compounds (preferably in the form of anions) ii). Oxidative polymerization of the opene monomer.

In embodiment 2 of method 1 according to the invention, method 1 is designed according to embodiment 1 thereof, wherein the organic moiety R bears no anionic groups. Preferably, the residue R does not bear any sulfonic acid groups or salts of such groups.

In embodiment 3 of method 1 according to the invention, method 1 is designed according to embodiments 1 or 2 thereof, wherein the organic moiety R is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group do.

In embodiment 4 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 3 thereof, wherein the reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa) or (VIb) , wherein X and Z comprise O, preferably a thiophene monomer of formula (VIa), wherein X and Z represent O, and among the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ 3 and one of the residues selected from the group consisting of R ⁵ and R ⁶ represents a hydrogen atom and the remaining residues represent an ether group having the formula IIa:

[Formula IIa]

-(CR ⁷ R ⁸ ) _n -OR ⁹

here,

R ⁷ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁷ is H;

R ⁸ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁸ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, and even more preferably a C ₂ - C ₂₀ -alkyl group.

In embodiment 5 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 3 thereof, wherein the reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa) or (VIb) , wherein X and Z comprise O, preferably a thiophene monomer of formula (VIa), wherein X and Z represent O, and among the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ with at least two and one of the residues selected from the group consisting of R ⁵ and R ⁶ , preferably at least three of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ and R ⁵ and R ⁶ One of the residues selected from the group consisting of represents a hydrogen atom, the remaining residues represent an alkyl group, preferably the remaining residues represent an alkyl group having the formula (IIb):

[Formula IIb]

-C _n H _2n+1

Here, n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15 and even more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group, wherein The ethyl group, n-butyl group and n-decyl group are particularly preferred, wherein the n-butyl group is most preferred.

Suitable examples of monomer units of formula Ia bearing a branched alkyl group or more than one alkyl group include compounds selected from the group consisting of compounds (A), (B), (C) and (D):

In embodiment 6 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 3, wherein the reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa) or (VIb), wherein , X and Z are O, preferably comprising a thiophene monomer of formula (VIa), wherein X and Z represent O and 3 of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ and one of the residues selected from the group consisting of R ⁵ and R ⁶ represents a hydrogen atom, and the other residue is a branched alkyl group or branched ether group, preferably a branched ether group, more preferably, having the formula IIc Represents a branched ether group:

[Formula IIc]

-(CR ¹⁰ R ¹¹ ) _n -OR ¹²

here,

R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹⁰ is H;

R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹¹ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain, even more preferably preferably an organic moiety having the formula IId:

[Formula IId]

-(CHR ¹³ ) _m -R ¹⁴

here,

m is 1, 2 or 3,

R ¹³ is H or a C ₁ -C ₁₂ alkyl group, preferably a C ₂ -C ₁₀ alkyl group, more preferably a C ₃ -C ₈ alkyl group, even more preferably a butyl group, provided that the structural unit -CHR ¹³ - only one of, R ¹³ is a C ₁ -C ₁₂ alkyl group;

R ¹⁴ is a C ₁ -C ₁₀ -alkyl group, preferably a C ₂ -C ₆ -alkyl group, or an aryl group.

In embodiment 7 of method 1 according to the present invention, method 1 is designed according to embodiment 6 thereof, wherein the polythiophene comprises a monomer unit selected from the group consisting of compounds (E), (F) and (G) It is a homopolymer or copolymer comprising:

With respect to embodiments 6 and 7 of the process according to the invention, organic compounds having more than two inorganic acid groups and having a molecular weight of more than 1,000 g/mol, such as polystyrene sulfonic acid (PSS), are used as component ii) may also be possible.

In embodiment 8 of method 1 according to the invention, method 1 is designed according to embodiments 1 to 7 thereof, wherein the reaction mixture comprises 3,4-ethylenedioxythiophene as component i) and X and Z are O at least one derivative of 3,4-ethylenedioxythiophene having the formula (VIa) represented, wherein at least one organic solvent iii) is an aprotic solvent iii), and in process step II), Oxidative polymerization to form a derivative copolymer of ethylenedioxythiophene and 3,4-ethylenedioxythiophene. Thus, the reaction mixture provided in process step I) comprises, as component i), 3,4-ethylenedioxythiophene and at least one 3,4-ethylenediox wherein at least one of the hydrogen atoms of the ethylene group is replaced by an organic moiety R derivatives of thiophene.

In embodiment 9 of method 1 according to the present invention, method 1 is designed according to embodiment 8 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula Ia':

[Formula Ia']

Here, R is preferably selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.

In embodiment 10 of method 1 according to the invention, method 1 is designed according to embodiment 9 thereof, wherein the organic moiety R is an ether group.

In embodiment 11 of method 1 according to the invention, method 1 is designed according to embodiment 10 thereof, wherein the ether group has the formula IIa:

[Formula IIa]

-(CR ⁷ R ⁸ ) _n -OR ⁹

here,

R ⁷ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁷ is H;

R ⁸ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ⁸ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, even more preferably a C ₂ -C ₂₀ -alkyl group.

In embodiment 12 of method 1 according to the invention, method 1 is designed according to embodiment 11 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula (III):

[Formula Ⅲ]

Here, R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₂ -C ₂₅ -alkyl group, even more preferably a C ₅ - C ₂₀ -alkyl group.

In embodiment 13 of method 1 according to the invention, method 1 is designed according to embodiment 12 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula (IV):

[Formula IV]

wherein m is an integer ranging from 0 to 24, preferably from 1 to 19 and more preferably from 4 to 14, and most preferably m is 9.

In embodiment 14 of method 1 according to the invention, method 1 is designed according to embodiment 9 thereof, wherein the organic moiety R is an alkyl group.

In embodiment 15 of method 1 according to the present invention, method 1 is designed according to embodiment 14 thereof, wherein the alkyl group has the formula IIb:

[Formula IIb]

-C _n H _2n+1

Here, n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15 and still more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group, wherein The ethyl group, n-butyl group and n-decyl group are particularly preferred, wherein the n-butyl group is most preferred.

In embodiment 16 of method 1 according to the invention, method 1 is designed according to embodiment 15 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the formula (V):

[Formula V]

Here, n is in the range of 0 to 19, preferably in the range of 1 to 14, and more preferably in the range of 2 to 9. It is particularly preferred that n is 2, 3 or 4, where n = 3 is most preferred.

In embodiment 17 of method 1 according to the invention, method 1 is designed according to embodiment 9 thereof, wherein the organic moiety R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group It is preferably a branched ether group having the formula (IIc):

[Formula IIc]

-(CR ¹⁰ R ¹¹ ) _n -OR ¹²

here,

R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹⁰ is H;

R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, more preferably a methyl group, or a C ₁ -C ₁₀ -alkoxy group, preferably a C ₁ -C ₅ - An alkoxy group, more preferably a methoxy group, wherein most preferably R ¹¹ is H;

n is an integer ranging from 0 to 10, preferably from 1 to 6 and more preferably from 1 to 3, wherein most preferably n is 1; and

R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain, even more preferably preferably an organic moiety having the formula IId:

[Formula IId]

-(CHR ¹³ ) _m -R ¹⁴

here,

m is 1, 2 or 3,

R ¹³ is H or a C ₁ -C ₁₂ alkyl group, preferably a C ₂ -C ₁₀ alkyl group, more preferably a C ₃ -C ₈ alkyl group, even more preferably a butyl group, provided that the structural unit -CHR ¹³ - only one of, R ¹³ is a C ₁ -C ₁₂ alkyl group;

R ¹⁴ is a C ₁ -C ₁₀ -alkyl group, preferably a C ₂ -C ₆ -alkyl group, or an aryl group.

In embodiment 18 of method 1 according to the present invention, method 1 is designed according to embodiment 17 thereof, wherein the polythiophene comprises a monomer unit selected from the group consisting of compounds (E), (F) and (G) It is a homopolymer or copolymer comprising:

In embodiment 19 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 18 thereof, wherein the reaction mixture provided in process step I) comprises 3,4-ethylenedioxythiophene and 3,4-ethylene in relative amounts of 5 to 95%, preferably 10 to 80%, more preferably 20 to 60%, in each case based on the total molar amount of derivatives of 3,4-ethylenedioxythiophene. derivatives of deoxythiophene.

In embodiment 20 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 18 thereof, wherein the reaction mixture provided in process step I) is based on the total weight of monomer units (i.e. , based on the total weight of 3,4-ethylenedioxythiophene-monomer units and monomer units based on derivatives of 3,4-ethylenedioxythiophene) in each case) based on derivatives of 3,4-ethylenedioxythiophene Thus, at least 30 wt %, preferably at least 40 wt % and more preferably at least 70 wt % monomer units.

In embodiment 21 of composition 1 according to the invention, composition 1 is designed according to embodiment 6 thereof, wherein the reaction mixture comprises, as component i), the following components:

α) at least one derivative of 3,4-ethylenedioxythiophene having the formula la';

[Formula Ia']

wherein R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group having the formula IIc as defined above;

β) at least one derivative of 3,4-ethylenedioxythiophene having the formula la';

[Formula Ia']

wherein R is an alkyl group having the formula IIb as defined above, wherein the thiophene derivative is 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxine, 2- Propyl-2,3-dihydrothieno-[3,4-b]-1,4-dioxine, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4- selected from the group consisting of dioxin, 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, 2-decyl-2,3-dihydrothieno[3 Preference is given to ,4-b][1,4]dioxine, wherein 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxine (butyl-EDOT) is particularly preferred,

and optionally

γ) 3,4-ethylenedioxythiophene.

In embodiment 22 of method 1 according to the invention, method 1 is designed according to embodiment 21 thereof, wherein the reaction mixture is in each case based on the total amount of monomers α), β) and γ) in the reaction mixture , 5 to 99 mol %, preferably 15 to 70 mol % and more preferably 30 to 50 mol % monomer units, based on monomer α) 5 to 95 mol %, preferably 30 based on monomer β) to 90 mol % and more preferably 50 to 70 mol % monomer units, and 0 to 50 mol %, preferably 0 to 35 mol % and more preferably 0 to 20 mol % monomer units, based on the monomer γ). wherein the sum of the amounts of monomers α), β) and γ) is up to 100 mol %. According to a particularly preferred embodiment of method 1, the reaction mixture does not comprise 3,4-ethylenedioxythiophene as comonomer.

In embodiment 23 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 22, wherein in process step I), process step II) or both process steps, the organic compound ii) is present in the form of a free acid.

In embodiment 24 of method 1 according to the present invention, method 1 is designed according to any one of embodiments 1 to 23 thereof, wherein the inorganic acid group is a sulfonic acid group (-SO ₂ OH), a sulfuric acid group (-O-SO ₂ OH), a phosphonic acid group (-PO(OH) ₂ ), or a phosphoric acid group (-O-PO(OH) ₂ ), preferably a sulfonic acid group (-SO ₂ OH).

In embodiment 25 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 24 thereof, wherein the organic compound ii) is an anionic surfactant.

In embodiment 26 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 25 thereof, wherein the anionic surfactant is sulfonic acid (R—SO ₂ OH), an ester of sulfuric acid (RO-SO ₂ OH) or a salt of one of these anionic surfactants, preferably a salt of sulfonic acid. In this context, it is particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (ie a compound having only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.

In embodiment 27 of method 1 according to the invention, method 1 is designed according to embodiment 26 thereof, wherein the anionic surfactant is dodecylbenzene sulfonic acid or a salt thereof.

In embodiment 28 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 27 thereof, wherein the total amount of thiophene monomer (component i) in the reaction mixture provided in process step I), Preferably the weight ratio of the total amount of 3,4-ethylenedioxythiophene and the derivatives of 3,4-ethylenedioxythiophene (component i) to the organic compound ii) is in the range of 1:30 to 1:0.1, preferably It is in the range of 1:20 to 1:0.2, and more preferably in the range of 1:5 to 1:0.5.

In embodiment 29 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 28 thereof, wherein at least one organic solvent iii), preferably at least one aprotic solvent iii) ) has a boiling point (determined at a pressure of 1013 mbar) in the range from 50 to 300 °C, preferably in the range from 60 to 250 °C and more preferably in the range from 70 to 220 °C.

In embodiment 30 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 29 thereof, wherein at least one organic solvent is an aprotic solvent iii), more preferably a polar It is an aprotic solvent.

In embodiment 31 of method 1 according to the invention, method 1 is designed according to embodiment 30 thereof, wherein the dielectric constant of the polar aprotic solvent iii) is less than 20, preferably less than 10 and more preferably is less than 7.

In embodiment 32 of method 1 according to the invention, method 1 is designed according to embodiments 30 or 31 thereof, wherein the polar aprotic solvent iii) is less than 4 D, preferably less than 2 D and more preferably has a dipole moment of less than 1.5 D.

In embodiment 33 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 32 thereof, wherein at least one organic solvent iii) is an aromatic hydrocarbon, ester, ether, alcohol and their is selected from the group consisting of mixtures.

In embodiment 34 of method 1 according to the invention, method 1 is designed according to embodiment 33 thereof, wherein the at least one organic solvent iii) comprises toluene, xylene, anisole, methyl benzoate, ethyl benzoate, Propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2- propylacetate, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or mixtures of one or two of these aprotic solvents with one or two additional solvents. In the case of mixtures of two or more organic solvents, it is particularly preferred that at least one of these solvents is an aprotic solvent iii).

In embodiment 35 of the method according to the invention, method 1 is designed according to any one of embodiments 1 to 34 thereof, wherein method 1 comprises the following additional steps:

III) adding monomer i), anion ii), aprotic solvent iii) and oxidizing agent iv) and other additives v) to the reaction mixture provided in process step I).

In embodiment 36 of the method according to the invention, method 1 is designed according to any one of embodiments 1 to 35, wherein method 1 comprises the following additional steps:

IV) diluting the composition obtained after process step II) or optionally obtained after process step III) or after process step IV) with a further organic solvent vi) different from solvent iii).

In embodiment 37 of the method according to the invention, method 1 is designed according to embodiment 36 thereof, wherein the weight ratio of the composition to the further solvent vi) ranges from 50:1 to 0.02:1.

In embodiment 38 of the method according to the invention, method 1 is designed according to embodiments 36 or 37 thereof, wherein the further organic solvent vi) is as defined in any one of embodiments 31 to 37 of method 1 , an organic solvent, preferably an aprotic solvent.

In embodiment 39 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 38 thereof, wherein the composition provided in process step I) comprises:

i) a thiophene monomer having the formula (VIa) or (VIb) in a total amount of 0.01 to 20 wt%, preferably 0.02 to 10 wt% and more preferably 0.1 to 5 wt%, preferably 3,4-ethylenedioxythiophene and a total amount within these ranges of derivatives of 3,4-ethylenedioxythiophene (thus corresponding to the total weight of derivatives of 3,4-ethylenedioxythiophene and 3,4-ethylenedioxythiophene);

ii) 0.01 to 15 wt %, preferably 0.02 to 10 wt % and more preferably 0.1 to 5 wt % of an organic compound;

iii) 50 to 99.98 wt %, preferably 70 to 99.86 wt % and more preferably 85 to 99.3 wt % of a solvent or solvent mixture, preferably an aprotic solvent or solvent mixture;

iv) 0.01 to 15 wt %, preferably 0.1 to 10 wt % and more preferably 0.5 to 5 wt % of components i) to iii) and other additives;

wherein the sum of the total weights of components i) to iv) is up to 100 wt %.

In embodiment 40 of method 1 according to the present invention, method 1 is designed according to any one of embodiments 1 to 39, wherein method 1 comprises the following additional steps:

V) adding a non-conductive oligomer or polymer, preferably a non-conductive oligomer or polymer binder, to the product obtained in process steps II), III) or IV).

In embodiment 41 of method 1 according to the present invention, method 1 is designed according to embodiment 40 thereof, wherein the non-conductive polymeric binder is polyolefin, polyvinyl acetate, polycarbonate, poly(meth)acrylate, poly Vinyl butyral, poly(meth)acrylic acid amide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, selected from the group consisting of polysulfone, polysilicon, epoxy resin, styrene-acrylate, vinyl acetate/acrylate or ethylene/vinyl acetate copolymer, polyvinyl alcohol, a cellulose derivative or a mixture comprising at least two of these polymers, Here, poly(meth)acrylate and polysilicon are particularly preferred non-conductive polymeric binders. Also suitable non-conductive polymeric binders are polyfunctional (meth)acrylates, such as dipentaerythritol penta-/hexaacrylate.

In embodiment 42 of method 1 according to the invention, method 1 is designed according to embodiment 41, wherein the poly(meth)acrylate is poly(methyl acrylate), poly(methyl methacrylate), poly( ethyl acrylate), poly(ethyl methacrylate), poly(n-propyl acrylate), poly(n-propyl methacrylate), poly(isopropyl acrylate), poly(isopropyl methacrylate), poly (n-butyl acrylate), poly(n-butyl methacrylate), poly(isobutyl acrylate), poly(isobutyl methacrylate), poly(tert-butyl acrylate), poly(tert-butyl methacrylate) acrylate), poly(2-ethylhexyl acrylate), poly(2-ethylhexyl methacrylate), poly(cyclohexyl acrylate), poly(cyclohexyl methacrylate), poly(phenyl acrylate), poly (phenyl methacrylate), poly(benzyl acrylate), poly(benzyl methacrylate) and copolymers of these polyacrylates or polymethacrylates.

In embodiment 43 of method 1 according to the invention, method 1 is designed according to any one of embodiments 40 to 42 thereof, wherein a non-conductive polymeric binder, preferably poly(meth)acrylate and/or poly The silicone is added in an amount such that the non-conductive polymeric binder and the polythiophene/organic compound complex are present in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

In embodiment 44 of method 1 according to the invention, method 1 is designed according to any one of embodiments 1 to 43, wherein the reaction mixture provided in process step I) comprises, based on the total weight of the composition, 2 wt. %, preferably less than 1 wt % and most preferably less than 0.1 wt % water.

A contribution to solving at least one of the objects according to the invention is also made by embodiment 1 of the composition 2, obtainable by method 1 according to any one of embodiments 1 to 44 thereof.

A contribution to solving at least one of the objects according to the invention is also made by embodiment 1 of a layer structure 1 comprising a substrate and an electrically conductive layer applied thereon, wherein the electrically conductive layer contains the following ingredients:

i) at least one polythiophene comprising monomer units of formula la or lb;

[Formula Ia] [Formula Ib]

here,

* indicates a bond to a neighboring monomer unit,

X, Z represents O or S,

R ¹ -R ⁶ independently of each other represent a hydrogen atom or an organic residue R,

provided that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ is an organic residue R, preferably a derivative of 3,4-ethylenedioxythiophene and at least one 3,4-ethylenedioxythiophene at least one copolymer of , wherein at least one of the hydrogen atoms of the ethylene group is substituted with an organic moiety R;

ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein the molecular weight of said organic compound or salt thereof is less than 1,000 g/mol, preferably less than 900 g/mol, more preferably 800 g /mol, even more preferably less than 700 g/mol, even more preferably less than 600 g/mol and even more preferably less than 500 g/mol.

Preferred polythiophenes or copolymers i) and anions ii) are polythiophenes or copolymers and anions, which have already been described in relation to composition 1 and method 1 according to the invention.

In embodiment 2 of the layer structure 1 according to the invention, the layer structure 1 is designed according to embodiment 1 thereof, wherein in the electrically conductive layer polythiophene i) for the organic compound ii) or a salt thereof, preferably The weight ratio of copolymer i) is in the range of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2 and more preferably in the range of 1:5 to 1:0.5.

In embodiment 3 of the layer structure 1 according to the invention, the layer structure 1 is designed according to embodiments 1 or 2, wherein the electrically conductive layer comprises:

iii) further comprising a non-conductive oligomer or polymer, preferably a non-conductive oligomer or polymer binder,

Here, preferred non-conductive oligomeric or polymeric binders are those already mentioned in embodiments 37 to 39 of the composition 1 according to the present invention.

In embodiment 4 of the layer structure 1 according to the invention, the layer structure 1 is designed according to embodiment 3 thereof, wherein the electrically conductive layer comprises a non-conductive polymeric binder iv), preferably poly(meth)acrylate and/or polysilicon and polythiophene/organic compound complex i)/ii) in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

In embodiment 5 of the layer structure 1 according to the invention, the layer structure 1 is designed according to embodiments 3 or 4 thereof, wherein the electrically conductive layer is at most 1×10 ¹⁰ Ohm/sq, preferably at most 5× It has a sheet resistance of 10 ⁹ Ohm/sq and more preferably up to 1×10 ⁸ Ohm/sq.

A contribution to solving at least one of the objects according to the invention is also made by an embodiment of a method for manufacturing a layer structure, said method comprising:

A) providing a substrate;

B) coating the substrate with composition 1 according to any one of embodiments 1 to 44 thereof or composition 2 according to embodiment 1 thereof;

C) at least partially removing the organic solvent iii), preferably the aprotic solvent iii) for the formation of the electrically conductive layer.

In embodiment 2 of method 2 according to the invention, method 2 comprises:

D) prior to performing process step B), applying an intermediate coating, such as an adhesive layer or a primer layer, onto the substrate.

A contribution to solving at least one of the objects according to the invention is also made by embodiment 1 of the layer structure 2, obtainable by the process 2 according to the invention.

In embodiment 2 of the layer structure 1 or layer structure 2 according to the invention, the layer structure is designed according to its corresponding embodiment 1, wherein the electrically conductive layer is at least 1 S/cm, preferably at least 2 S /cm and most preferably at least 5 S/cm.

A contribution to solving at least one of the objects according to the invention is an electronic component, in particular an organic light-emitting diode, comprising the layer structure 1 according to embodiment 1 or 2 thereof or the layer structure 2 according to embodiment 1 thereof; This is achieved by embodiment 1 of an organic solar cell or capacitor.

A contribution to solving at least one of the objects according to the invention is also the embodiment 1 thereof for producing an antistatic coating or for producing an electrically conductive layer in an electronic component, in particular an organic light emitting diode, an organic solar cell or a capacitor by the use of composition 1 according to any one of to 46 or composition 2 according to embodiment 1.

organic compounds ii)

The organic compound i) having one or two inorganic acid groups present in the composition or layer structure according to the invention or present in the reaction mixture provided in process step I) of the process according to the invention i) or a salt thereof is preferably an anion Anionic surfactants, wherein the anionic surfactants include organic sulfonic acids such as organic phosphonic acids, organic phosphoric acids, sulfonic acids, such as alkyl-aryl-sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and their salts or mixtures. Each of the following anionic surfactants may contain mixtures of compounds of varying lengths of alkyl chains:

- Suitable alkyl sulfates are C such as sodium dodecyl sulfate, lithium dodecyl sulfate, ammonium dodecyl sulfate, sodium tetradecyl sulfate, sodium 7-ethyl-2-methyl-4-undecyl sulfate and sodium 2-ethylhexyl sulfate ₈ -C ₁₈ alkyl sulfates, but are not limited thereto.

- Suitable alkyl ether sulfates include, but are not limited to, C ₈ -C ₁₈ alkyl ether sulfates such as sodium laureth sulfate and sodium myreth sulfate.

- Suitable alkyl sulfonates include, but are not limited to, C ₈ -C ₁₈ alkyl sulfonates such as sodium tetradecyl sulfonate, sodium octadecyl sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate and the corresponding sulfonic acids. it is not going to be

- Suitable aryl sulfonates or sulfonic acids, optionally substituted with alkyl or aryl substituents, are C ₂ such as sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid, ethylbenzene sulfonic acid and dodecylbenzene sulfonic acid isopropyl amine salts -C ₁₈ alkylbenzene sulfonate or sulfonic acid; sodium butyl naphthalene sulfonate and sodium hexyl naphthalene sulfonate, especially sodium dodecylbenzene sulfonate or C ₂ -C ₁₈ alkyl naphthalene sulfonate or sulfonic acid such as dodecylbenzene sulfonic acid. When optionally substituted with an alkyl substituent, the aryl sulfonate or sulfonic acid may be located at any point along the alkyl chain, eg, at a primary, secondary or tertiary carbon. Suitable alkyl ester sulfonates or sulfonic acids are C ₂ -C , such as methyl ester sulfonate, sodium dodecyl methyl ester α-sulfonate, sodium tetradecyl methyl ester α-sulfonate and sodium hexadecyl methyl ester α-sulfonate. ₁₈ alkyl methyl ester sulfonate or sulfonic acid. A sulfate, sulfonate or sulfonic acid group may be located at any point along the alkyl chain or aryl ring, for example on the primary, secondary or tertiary carbon.

- Surfactants bearing two sulfonic acid groups, such as C ₂ -C ₁₆ alkyl diphenyl oxide disulfonates or disulfonic acid, such as sodium dodecyl diphenyloxide disulfonate are also suitable.

- Suitable organic phosphonic acids are phenyl phosphonic acid, 11-hydroxyundecyl phosphonic acid, 2,4-xylyl phosphonic acid, 4-ethylphenyl phosphonic acid, octyl phosphonic acid, octadecyl phosphonic acid, undecyl phosphonic acid, dodecyl phosphonic acid, p-(diphenylmethyl) phosphonic acid, 11-phosphono undecanoic acid and p-(1-naphthalenylmethyl) phosphonic acid, or diphosphonic acid such as (12-phosphonododecyl) monovalent phosphonic acids such as phosphonic acid and 1,8-octane diphosphonic acid.

However, it is particularly preferred that the anionic surfactant is a monovalent sulfonic acid, and dodecylbenzene sulfonic acid or a salt thereof is particularly preferred.

Additives iv)

Suitable additives iv) which may also be present in the composition according to the invention include oxidizing agents (preferably in their reduced form), conductivity-improving agents, adhesion promoters, binders and crosslinking agents:

- Additives for improving conductivity are, for example, compounds such as tetrahydrofuran, lactone group-containing compounds such as butyrolactone, valerolactone, amide group- or lactam group-containing compounds such as caprolactam, N- Methyl caprolactam, N,N-dimethyl acetamide, N-methyl acetamide, N,N-dimethyl formamide (DMF), N-methyl formamide, N-methyl formanilide, N-methyl pyrrolidone (NMP) ), N-octyl pyrrolidone, pyrrolidone, sulfones and sulfoxides such as, for example, sulfolane (tetramethylene sulfone), dimethyl sulfoxide (DMSO), sugars or sugar derivatives such as, for example, sucrose, glucose, fructose, lactose, sugar-based surfactants such as Tween or Span 60, sugar alcohols such as sorbitol, mannitol, furan derivatives such as, for example, 2-furan carboxylic acid, 3-furan carboxylic acid, and/or di- or polyhydric alcohols such as, for example, ethylene glycol, glycerol or di- or triethylene glycol. Tetrahydrofuran, N-methyl formamide, N-methyl pyrrolidone, ethylene glycol, dimethyl sulfoxide or sorbitol are particularly preferably used as conductivity-raising additives.

- Suitable adhesion promoters are compounds such as, for example, organofunctional silanes or hydrolysates thereof, for example 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercapto propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane.

- binders, organic binders, such as polyolefins, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylic acid esters, polyacrylic acid amides, polymethacrylic acid, which are particularly soluble in organic solvents and which can also be added to the composition Ester, polymethacrylic acid amide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinyl pyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, polysulfone, poly silicones, epoxy resins, styrene-acrylates, vinyl acetate/acrylate and ethylene/vinyl acetate copolymers, polyvinyl alcohol or cellulose derivatives. Also suitable as binders are copolymers of the aforementioned polymers. In particular in the case of polythiophenes comprising a thiophene monomer bearing an alkyl group as moiety R, it is particularly preferred that the composition further comprises a non-conductive oligomeric or polymeric binder, in particular poly(meth)acrylate and/or polysilicon. .

- suitable crosslinking agents are melamine compounds, capped isocyanates, alkoxysilane hydrolysates based on functional silanes, for example tetraethoxysilane, for example tetraethoxysilane, or 3-glycidoxypropyl tri epoxysilanes such as alkoxysilanes.

Method for preparing the composition according to the invention

In the process according to the invention, the thiophene monomer is oxidatively polymerized in the presence of an organic compound ii) (preferably in the form of an anion) and an aprotic solvent iii). An oxidizing agent iv) suitable for the oxidative polymerization of pyrrole may be used as an oxidizing agent. For practical reasons, inexpensive and easy to handle oxidizing agents may be used, for example iron(III) salts such as FeCl ₃ , Fe(ClO ₄ ) ₃ and iron(III) salts of inorganic and organic acids containing organic radicals. As examples of iron(III) salts of sulfuric acid hemiesters of C ₁ -C ₂₀ alkanols, for example Fe(III) salts of lauryl sulfate, iron(III) salts of inorganic acids containing organic radicals are is mentioned as iron(III) salts of organic acids, for example Fe(III) salts of C ₁ -C ₂₀ alkyl sulfonic acids, such as methane- and dodecane-sulfonic acids; Fe(III) salts of aliphatic C ₁ -C ₂₀ carboxylic acids, such as 2-ethylhexyl carboxylic acid; Fe(III) salts of aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid and perfluorooctanoic acid; Fe(III) salts of aliphatic dicarboxylic acids such as oxalic acid and above all aromatic sulfonic acids optionally substituted with C ₁ -C ₂₀ alkyl groups, such as benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid is mentioned The iron(III) salts of organic acids have the great application advantage that they are partially or completely soluble in organic solvents, in particular water-immiscible organic solvents. For example, tert-butyl peroxide, diisobutyryl peroxide, di-n-propyl peroxydicarbonate, didecanoyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-amyl Organic peroxides, such as peroxides, may also be used as oxidizing agents. For example, organic azo compounds such as 2,2'-azodiisobutyronitrile may also be used. Particularly preferred oxidizing agents are organic, metal-free oxidizing agents such as organic peroxides, with dibenzoyl peroxide being most preferred.

In theory, for the oxidative polymerization of thiophene monomers, 2.25 equivalents of oxidizing agent per mole of thiophene are required (see, e.g., J. Polym. Sc., Part A, Polymer Chemistry, vol. 26, p. 1287). 1988), see). However, in the prior art, the oxidizing agent is usually used in a certain excess, for example in an excess of 0.1 to 2 equivalents per mole of thiophene.

In process step II) of the process according to the invention, the thiophene monomer is oxidatively polymerized by reduction of an oxidizing agent to a reduction product and oxidation of the thiophene monomer - in the presence of organic compound ii) to a cationic polythiophene-air Forming a composition preferably comprising coalescence i) and a reduction product, wherein said polymerization preferably takes place at a temperature in the range from 0 °C to 100 °C. In this context, it is particularly preferred that the reaction temperature ranges from 25° C. to a temperature that is below the lowest boiling point of the solvent comprised in the reaction mixture.

The anion ii) present in the reaction mixture provided in process step I) serves as a counterion compensating for the positive charge of the polythiophene i), preferably the copolymer i). Anion ii) and polythiophene i) are preferably present in the form of a polythiophene/anion-complex. In this context, it is also preferred that, in process step II), a composition comprising polythiophene i) and anion ii) is obtained in the form of such a complex, wherein the composition is prepared in an aprotic solvent iii) in which this complex is dispersed. It is particularly preferred to be present in the form of a dispersion comprising

Test Methods

Determination of Conductivity

Electrical conductivity means the reciprocal of specific resistance. The resistivity is calculated by multiplying the surface resistance of the conductive polymer layer by the layer thickness. The surface resistance is determined for conductive polymers according to DIN EN ISO 3915. Specifically, on a 50 mm×50 mm sized glass substrate thoroughly cleaned by the substrate cleaning process described above, the composition to be studied was applied as a homogeneous film by a spin coater. In this procedure, the coating composition is applied to a substrate using a pipette to completely cover the area and is spun off directly by spin coating. Spin conditions for the coating composition are approximately 20 seconds at approximately 1,000 rpm in air. Thereafter, a drying process is carried out on a hot-plate (130° C. in atmosphere, 10 minutes). A silver electrode with a length of 2.0 cm at a spacing of 2.0 cm is deposited on the polymer layer through a shadow mask. A square region of the layer between the electrodes is then electrically isolated from the rest of the layer by scraping the two stripes with a scalpel. The surface resistance is measured between the Ag electrodes using an ohmmeter (Keithley 614). The thickness of the polymer layer was determined using a Stylus Profilometer (Dektac 150, Veeco) at the scratched area.

Determination of moisture content

The water content of the composition according to the invention can be determined by Karl Fischer titration. For this purpose a Metrohm 787 KF Titrino with a 703 titration stand is used. The titration vessel is filled with analytical methanol and immersed approximately 1 cm of the platinum electrode. Approximately 5 ml of Hydranal buffer acid is then pipetted. The titration cell is automatically dried by starting the KFT program. When the message “KFT conditioned” appears, preparation is complete. Approximately 5 ml of the composition to be analyzed is then introduced into the titration vessel using a syringe, and the exact mass of the dispersion used is determined by weighing the syringe. The titration is then started. The measured value is determined as the average of three individual measured values.

solid content

The solids content is determined gravimetrically using a precision balance (Mettler AE 240). First, weigh the empty weighing bottle with the lid (weight A). About 3 g of the dispersion to be analyzed is then quickly filled into the bottle, capped and reweighed to determine the correct total weight B. The bottle is then placed in an unlit fume hood at room temperature for approximately 3 hours to allow the volatile solvents to evaporate. In the second step, the bottles are placed in a ventilated drying oven (Memmert UNB200) at 160° C. for 16-17 hours. When the sample bottle is removed from the oven, it is important to immediately cover it with a glass lid due to the hygroscopicity of the dry dispersion material. After 10-15 minutes of cooling period, weigh the bottle again, including the cap, to determine the weight C.

Calculation of solids content: wt% solids content = 100×(C-A)/(B-A)

The result is the average of the two measurements.

Preparation of Films on PET Substrates

The dispersion is applied to the PET substrate at room temperature using Erichsen's manual doctor blades with a gap separation of 12 μm. The gap separation of the manual doctor blade in this context determines the thickness of the formed wet film, also called wet film thickness. The coating or film formed in this way is then dried in a drying oven at 130° C. for 5 minutes. Prior to any further processing, the coated PET substrate is cooled to room temperature.

Determination of surface resistance

Surface resistance is measured with a Staticide ACL 800 Digital Megohmmeter at 100 V setting. Two measurements are made at different positions on the sheet, and the lowest value is taken as the result. The highest measurable surface resistance is 2×10 ¹¹ Ω/sq. Values above that threshold will be considered out of range, but will still be expressed as 2×10 ¹¹ Ω/sq.

Determination of the stability of dispersions in organic solvents

The stability of the dispersion is determined by slowly adding the stated amount of solvent to the initial dispersion over 5 minutes. The mixture is stirred slowly during the course of solvent addition and for an additional 15 minutes. The mixture is stored at room temperature for 24 hours without mechanical disturbance. The resulting mixture is classified into three categories after visual evaluation:

+ Stable, uniform dispersion free of random particles

0 Visible Small Particles

- large particles and/or significant gelation and/or phase separation

Example

Example 1:

(Reference example for the synthesis of 2-[(decyloxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxin)

The synthesis is carried out under dry and inert conditions.

THF (6.6 L) and 18-Crown-6 (22.0 g, 88 mmol) are added to the reaction vessel. NaH (166.4 g, 4.15 mol), a 60% suspension in oil, is added under stirring and the mixture is stirred at room temperature. At 0 °C, a solution of EDOT-MeOH (551 g, 3.2 mol) in THF is added to the NaH solution. After addition of the solution, the reaction mixture is stirred at room temperature for 1.5 hours, then at 50° C. for 1 hour. The reaction mixture is cooled to 0 °C, and a solution of 1-bromo-decane (936.7 g, 4.2 mol) is stirred at room temperature for 1 h and at 50 °C for 15 h. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product is purified by column chromatography.

The reaction product (2-[(decyloxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxine, CAS: 210476-55-4) is 74-80 It is obtained as a yellow oil in a yield of %.

Example 2:

(Comparative example according to the teaching of WO-A-2012/059215)

A 1 L 3-necked round bottom flask equipped with a mechanical stirrer was prepared with 294 g of anisole (Aldrich), 9.4 g of dibenzoyl peroxide (39 mmol; Aldrich), 8.25 g of a sulfonated block-copolymer ( Kraton ^Nexar® MD) and 7.2 g of para-toluene sulfonic acid (38 mmol, Aldrich). After heating to 60° C., 4.95 g of 3,4-ethylenedioxythiophene (35 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) dissolved in 20 g of anisole is added over 40 min. The dispersion is stirred at 60° C. for another 3 h and then cooled to room temperature. This dispersion is called dispersion 2A.

20 g of the dispersion obtained after filtration and 20 g of butyl acetate are mixed in a 50 ml glass bottle and subjected to 2 min sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This sample is called Dispersion 2B.

Analysis of Dispersion 2B:

Solids content: 2.5% (wt)

Using a wire-bar, a 12 μm wet film was deposited with dispersion 2B on a substrate and dried in an oven at 130° C. for 15 minutes. The conductive layer has the following characteristics:

Conductivity (glass): 7.7 S/cm

Sheet resistance (12 μm on PET): 17,000 Ohm/sq

Example 3 (according to the invention)

In Example 3, the following complexes were prepared:

Dispersion A:

A 100 ml 3-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen inlet was prepared with 29.7 g of anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.7 g of dodecylbenzene. Charged with sulfonic acid (11.5 mmol; Aldrich). After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in Example 1 (5 mmol) ) is added. The dispersion is stirred at 60° C. under nitrogen for an additional 3 hours. Then 35 g of anisole is added. After cooling to room temperature, the dispersion is left overnight. This dispersion is called dispersion 3A.

Dispersion 3B:

5 g of dispersion 3A and 5 g of butyl acetate are mixed in a 20 ml glass bottle and subjected to 1 min sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called Dispersion 3B.

Analysis of Dispersion 3B:

Solids content: 2.4% (wt)

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The film has the following characteristics:

Sheet resistance (12 μm on PET): 20,000 Ohm/sq

Dispersion 3C:

2.5 g of dispersion 3A, 2.5 g of anisole and 5 g of butyl acetate are mixed in a 20 ml glass bottle and subjected to 1 min sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called Dispersion 3C.

Analysis of Dispersion 3C:

Solids content: 1.2% (wt)

Moisture content: 0.04%

Ion-content is measured by inductively coupled plasma light emission spectroscopy:

Na content: 24 ppm

Ca content: 0.6 ppm

Mg content: 0.06 ppm

K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd are below the detection limit of 0.025 ppm.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. This film has the following characteristics:

Sheet resistance (12 μm on PET): 16,000 Ohm/sq

Transmittance (including PET): 83.3%

Haze (including PET): 0.58

Dispersion 3C is deposited on glass by spin-coating and dried on a hot plate at 130° C. for 10 minutes. Conductivity is measured according to the test method described above.

This film has the following characteristics:

Conductivity: 9.4 S/cm

Example 4 (according to the invention)

(In Example 4, the concentration of dodecylbenzenesulfonic acid was reduced)

A 100 ml 3-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen inlet was prepared with 29.7 g of anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.08 g of dodecylbenzene. Charged with sulfonic acid (9.6 mmol; Aldrich). After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in Example 1 (5 mmol) ) is added. The dispersion is stirred at 60° C. under nitrogen for an additional 3 hours. Then 35 g of anisole is added. After cooling to room temperature, the dispersion is left overnight. This dispersion is called dispersion 4A.

5 g of dispersion 4A, and 5 g of butyl acetate are mixed in a 20 ml glass bottle and subjected to 1 min sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called Dispersion 4C.

Analysis of Dispersion 4C:

Solids content: 2.1% (wt)

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. This film has the following characteristics:

Sheet resistance (12 μm on PET): 12,000 Ohm/sq

Example 5 (according to the invention)

(In Example 5, the concentration of dodecylbenzenesulfonic acid was further reduced)

A 100 ml 3-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen inlet was prepared with 29.7 g of anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 2.2 g of dodecylbenzene. Charged with sulfonic acid (6.8 mmol; Aldrich). After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in Example 1 (5 mmol) ) is added. The dispersion is stirred at 60° C. under nitrogen for an additional 3 hours. Then 35 g of anisole is added. After cooling to room temperature, the dispersion is left overnight. This dispersion is called dispersion 5A.

Example 6

Dispersion 2A and Dispersion 5A are compared with respect to their solvent compatibility. Samples are mixed with additional solvents as shown in Table 1 and then subjected to ultrasound for 1 minute.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The sheet resistance is determined.

Dilution of Inventive Dispersion 5A and Reference Dispersion 2A with Different Solvents and Sheet Resistance of Each Film Example polythiophene dispersion added solvent SR(Ohm/sq) 6A (invention) 5 g dispersion 5A 5 g DMSO 1.5×10 ⁵ 6B (invention) 5 g dispersion 5A 5 g n-butanol 2.2×10 ⁴ 6C (reference) 5 g dispersion 2A 5 g DMSO 1.8×10 ¹¹ 6D (Reference) 5 g dispersion 2A 5 g n-butanol 6.9×10 ¹⁰

Table 1 shows that Dispersion 5A of the present invention provides low sheet resistance values of less than 1.5×10 ⁵ Ohm/sq for various solvents, while Dispersion 2A provides values up to 10 ¹¹ Ohm/sq.

Example 7

A 2.5% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) is prepared. This solution is mixed with dispersion 2B in different ratios. Since both solutions have the same solids content, the ratio of solution/dispersion corresponds to the ratio of solids in the resulting film.

Additionally, a 2.4% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) is prepared. This solution is mixed with dispersion 3B in different ratios. Since both solutions have the same solids content, the ratio of solution/dispersion corresponds to the ratio of solids in the resulting film.

Using a wire-bar, 12 μm wet films of all 8 mixtures were deposited on PET substrates and dried in an oven at 130° C. for 15 minutes.

Sheet resistance and haze of polythiophene/poly(isobutyl methacrylate) coating on PET film dispersion Ratio of polythiophene complex to poly(isobutyl methacrylate) in dry film (w:w) Solids content of mixture [%] sheet resistance
(Ohm/sq) Haze (%) 2B (reference) 1 : 9 2.5 6.3×10 ⁷ 1.2 2B (reference) 1: 4 2.5 5.0×10 ⁶ 6.7 2B (reference) 1: 2 2.5 6.6×10 ⁵ 13.3 2B (reference) 1:1 2.5 1.3×10 ⁵ 17.5 3B (invention) 1 : 9 2.4 1.6×10 ⁶ 0.42 3B (invention) 1: 4 2.4 1.7×10 ⁵ 0.49 3B (invention) 1: 2 2.4 5.5×10 ⁴ 0.55 3B (invention) 1:1 2.4 2.6×10 ⁴ 0.8

Table 2 shows that Dispersion 3B of the present invention results in lower sheet resistance and lower haze when blended with poly(isobutyl methacrylate) compared to Reference Dispersion 2B.

Example 8 (according to the invention)

In Example 8, the following complex was prepared:

Dispersion 8A:

A 100 ml 3-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen inlet was prepared with 29.7 g of anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g of dodecylbenzene. Charged with sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C., 0.42 g of 3,4-ethylenedioxythiophene (3 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.38 g of 2-butyl-2,3-dihydrothier No[3,4b][1,4]dioxine (7 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) is added. The dispersion is stirred at 60° C. under nitrogen for an additional 3 hours. Then 35 g of anisole is added. After cooling to room temperature, the dispersion is left overnight. This dispersion is called dispersion 8A.

Dispersion 8B:

5 g of dispersion 6A, 3 g of anisole and 2 g of butanol are mixed in a 20 ml glass bottle and subjected to 1 min sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 8B.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. This film has the following characteristics:

Sheet resistance (12 μm on PET): 17,400 Ohm/sq

Haze (12 μm on PET): 0.7

Example 9 (according to the invention)

The synthesis of Example 8 is 0.846 g of 3,4-ethylenedioxythiophene (6 mmol) and 0.79 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (4 mmol) was repeated. All other parameters remain unchanged. The final material obtained after sonication is called Dispersion 9B.

Example 10 (according to the invention)

The synthesis of Example 8 is 0.705 g of 3,4-ethylenedioxythiophene (5 mmol) and 0.98 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (5 mmol) is repeated. All other parameters remain unchanged. The final material obtained after sonication is called Dispersion 10B.

Example 11 (according to the invention)

The synthesis of Example 8 is 0.56 g of 3,4-ethylenedioxythiophene (4 mmol) and 1.18 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (6 mmol) was repeated. All other parameters remain unchanged. The final material obtained after sonication is called dispersion 11B.

Example 12 (according to the invention)

The synthesis of Example 8 is repeated using 2-butyl-2,3-dihydrothieno-[3,4b][1,4]dioxine in an amount of 10 mmol. 3,4-ethylenedioxythiophene was not used. All other parameters remain unchanged. The dispersion obtained after cooling to room temperature and standing overnight is called dispersion 12A. The final material obtained after sonication is called Dispersion 12B.

Using a wire-bar, a 12 μm wet film was deposited from dispersions 9B to 12B according to Example 8 on a PET substrate and dried in an oven at 130° C. for 15 minutes. Films are characterized by their sheet resistance and haze.

The ion-content of 12B was determined by inductively coupled plasma light emission spectroscopy:

Na content: 1.4 ppm

Ca content: 2.8 ppm

Mg content: 0.02 ppm

K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd are below the detection limit of 0.025 ppm. Table 3 summarizes the results of dispersions 2B and 8B-12B for sheet resistance and haze.

Sheet Resistance and Haze of Films Made with Dispersions 2B and 8B-12B dispersion Side chains in EDT-derivatives Amount of EDT-derivatives
[mmol] amount of EDT
[mmol] counter ion sheet resistance
(Ohm/sq) haze
(%) 2B doesn't exist - 35 Nexar ^® MD 17,000 0.6 9B n-butyl 4 6 DBSA 4,100 6.1 10B n-butyl 5 5 DBSA 7,300 3.1 11B n-butyl 6 4 DBSA 14,400 0.7 8B n-butyl 7 3 DBSA 17,400 0.7 12B n-butyl 10 0 DBSA 80,000 0.5

Example 13 (according to the invention)

A solution of poly(isobutylmethacrylate) (PIBM) is prepared. For this purpose, 13.6 g of poly(isobutyl methacrylate) are dissolved in a mixture of 220 g of anisole, 132 g of butyl acetate and 8 g of butanol.

Series 1: of blends

A series of blends of PIBM solutions and dispersions 2B and 8B-12B are prepared. 9 g of PIBM solution is mixed with 0.34 g of dispersion 12B and 0.55 g of anisole, 0.33 g of butyl acetate and 0.22 g of butanol. The mass ratio of non-conducting PIBM and polythiophene/DBSA complex is 36:1. In the same way, 0.34 g of dispersions 2B and 8B to 11B are blended with 9 g of PIBM solution and additional solvent.

Series 2: in the blend

A second series of blends are prepared. 4 g of PIBM solution is mixed with 0.29 g of Dispersion 12B and 0.35 g of anisole, 0.21 g of butyl acetate and 0.14 g of butanol. The mass ratio of non-conducting PIBM and polythiophene/DBSA complex is 19:1. In the same way, 0.29 g of dispersions 2B and 8B to 11B are blended with 4 g of PIBM solution and additional solvent.

Using a wire-bar, 12 μm wet films of dispersions in series 1 and 2 were deposited on PET substrates and dried in an oven at 130° C. for 15 minutes. Films are characterized by their sheet resistance. Table 4 summarizes the results.

Sheet resistance of films made with dispersions 2B and 8B-12B with added PIBM ( ¹⁾ : not according to the invention) dispersion Side chains in EDT-derivatives Amount of EDT-derivatives
[mmol] amount of EDT
[mmol] counter ion Sheet resistance in PIBM (1:19) and blends
(W/sq) Sheet resistance in blends with PIBM (1:36)
(W/sq) 2B ¹⁾ doesn't exist --- 35 Nexar ^® MD 2×10 ¹¹ 2×10 ¹¹ 9B n-butyl 4 6 DBSA 4×10 ¹⁰ 2×10 ¹¹ 10B n-butyl 5 5 DBSA 3×10 ⁹ 1×10 ¹⁰ 11B n-butyl 6 4 DBSA 4×10 ⁷ 1×10 ¹⁰ 8B n-butyl 7 3 DBSA 1×10 ⁷ 2×10 ⁷ 12B n-butyl 10 0 DBSA 1×10 ⁷ 1×10 ⁷

Table 4 clearly shows the advantages of polythiophenes comprising alkyl-EDOT.

Example 14 (according to the invention)

The dispersion obtained in Example 12A is diluted with various solvents.

Table 5 shows the solvent mixture.

Example 14B:

5 g of dispersion 12B are mixed with 3 g of anisole and 2 g of n-butanol. The resulting solvent mixture contains 80% anisole (w/w) and 20% n-butanol (w/w). Using a wire-bar, a 12 μm wet film of the dispersion was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The solids content is 2.2%. The sheet resistance is 8×10 ⁴ Ohm/sq.

Example 14C:

5 g of the dispersion is mixed with 10 g of anisole and 5 g of n-butanol. The resulting solvent mixture contains 75% anisole and 25% n-butanol. The solids content is 1.1%. Using a wire-bar, a 12 μm wet film of the dispersion was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The sheet resistance is 16×10 ⁴ Ohm/sq.

Examples 14D, 14E, 14F and 14G were prepared accordingly.

Table 5 shows the composition and the resulting sheet resistance:

Blend of Dispersion 12A with various solvents dispersion density
[wt%] anisole butyl acetate toluene ethyl acetate n-butanol isopropanol PGME sheet resistance
(W/sq) 14B 2.2 80 20 8×10 ⁴ 14C 1.1 75 25 16×10 ⁴ 14D 1.1 50 50 16×10 ⁴ 14E 1.1 25 25 50 11×10 ⁴ 14F 2.2 50 30 20 8×10 ⁴ 14G 1.1 40 10 25 25 25×10 ⁴

In all six cases, a homogeneous dispersion is obtained which does not form particles or precipitates. Table 5 also clearly shows the advantages of polythiophenes comprising alkyl-EDOT.

Example 15 (according to the invention)

A 100 ml 3-neck round bottom flask equipped with a mechanical stirrer, condenser and nitrogen inlet was prepared with 29.7 g of anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g of dodecylbenzene. Charged with sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C., 0.56 g of 2-decyl-2,3-dihydrothieno[3,4b][1,4]dioxine (2 mmol; DecylEDOT; CAS 126213-55-6) and 1.58 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4) is added. The dispersion is stirred at 60° C. under nitrogen for a separate 3 hours. Then 35 g of anisole is added. After cooling to room temperature, the dispersion is left overnight. This dispersion is called dispersion 15A.

Dispersion 15B:

5 g of dispersion 15A, 3 g of anisole and 2 g of butanol are mixed in a 20 ml glass bottle and subjected to 1 min of sonication (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called Dispersion 15B.

Solids content: 2.4%

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. This film has the following characteristics:

Sheet resistance (12 μm on PET): 64,000 Ohm/sq

Haze (12 μm on PET): 0.8

Example 16 (according to the invention)

Poly(n-butylacrylate) is an example of a polyacrylate with a low glass-transition temperature (Tg = -54°C). Poly(n-butylacrylate) in toluene (CAS 9003-49-0; 25 wt % in toluene, M _w 99000 g/mol; Sigma Aldrich 181404) is blended with Dispersion 15B. Table 6 shows the blending ratios of the three mixtures.

Using a wire-bar, a 12 μm wet film was deposited for each mixture on a PET substrate and dried in an oven at 130° C. for 15 minutes. The sheet resistance is measured.

Blend of Dispersion 15B with poly(n-butylacrylate) and their sheet resistance Sample Mass of polybutyl-acrylate solution (25%) in toluene Mass of Dispersion 15B (2.4%) Mass of added toluene Ratio of polybutylacrylate:polythiophene complex in dry film sheet resistance
[Ohm/sq] 16A 5 g 5.2 g 0 g 90:10 5.5×10 ⁷ 16B 5 g 4.0 g 1.2 g 92.5:7.5 8.2×10 ⁸ 16C 5 g 2.0 g 3.2 g 97.5:3.7 6.6×10 ⁹

Example 17

(Reference example for the synthesis of 3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin)

The synthesis is carried out under dry and inert conditions.

THF (60 mL) and 18-Crown-6 (0.200 g, 0.8 mmol) are added to the reaction vessel. NaH (1.512 g, 37.8 mmol) as a 60% suspension in oil is added under stirring and the mixture is stirred at room temperature. At 0 °C, a solution of EDOT-MeOH (5.00 g, 29.0 mmol) in 20 mL THF is added to the NaH solution. After addition of the solution, the reaction mixture is stirred at room temperature for 2.5 hours and then at 55° C. for 0.5 hours. The reaction mixture is cooled to 0 °C and a solution of 2-ethylhexyl bromide (7.300 g, 37.8 mmol) in 20 mL THF is added. The reaction mixture is stirred at room temperature for 1 hour and at 50° C. for 40 hours. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product is purified by column chromatography.

The reaction product (3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in 15% yield.

Example 18

(Reference example for the synthesis of 3-(1-phenylethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine)

The synthesis is carried out under dry and inert conditions.

DMSO (50 mL), KOH (3.254 g, 58 mmol), (1-bromoethyl)benzene (6.700 g, 37.8 mmol), and EDOT-MeOH (5.00 g, 29.0 mmol) are added to a reaction vessel. The resulting reaction mixture is stirred at 20° C. for 24 hours. After the reaction is complete, the reaction mixture is poured into deionized water (1000 mL) and stirred for 1 hour. The volume of the resulting mixture is halved by vacuum distillation. The mixture is extracted three times with ethyl acetate (150 mL), the combined organic phases are washed with brine (150 mL), dried over MgSO ₄ and the solvent removed in vacuo. The crude product is purified by column chromatography.

The reaction product (3-(1-phenylethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in 49% yield.

Example 19

A 250 mL 3-necked round bottom flask equipped with a mechanical stirrer was charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid. (9.3 mmol, Aldrich). After heating to 60° C., 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (6 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g of product (4 mmol) obtained from the reaction in Example 17 are added over 40 minutes. The dispersion is stirred at 60° C. for another 3 h and then cooled to room temperature.

50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol are added to a 100 ml flask and mixed through gentle stirring of the resulting dispersion.

This is called dispersion 19.

Analysis of Dispersion 19:

Solids content: 2.4% (wt)

Sheet resistance (12 μm on PET): 210000 Ohm/sq

The ion-content of dispersion 19 is determined by inductively coupled plasma light emission spectroscopy:

Na 0.324 ppm

Fe 0.043 ppm

Cu 0.000 ppm

Pb 0.000 ppm

B 0.010 ppm

Mo 0.370 ppm

Al 0.000 ppm

Cr 0.028 ppm

Co 0.000 ppm

Mn 0.000 ppm

Ni 0.000 ppm

V 0.000 ppm

Zn 0.514 ppm

Ca 0.172 ppm

K 0.000 ppm

Mg 0.077 ppm

Cd 0.012 ppm

Example 20

A 250 mL 3-necked round bottom flask equipped with a mechanical stirrer was charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid. (9.3 mmol, Aldrich). After heating to 60° C., 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (10 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) is added over 40 minutes. The dispersion is stirred at 60° C. for a further 3 h and then cooled to room temperature.

50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol are added to a 100 ml flask and mixed through gentle stirring of the resulting dispersion.

This is called dispersion 20.

Analysis of Dispersion 20:

Solids content: 2.2% (wt)

Sheet resistance (12 μm on PET): 70000 Ohm/sq

Example 21

Dispersion 19 and Dispersion 20 are tested for their solvent compatibility. 1 g of the named dispersion is mixed with 9 g of additional solvent as shown in Table 7 by gentle stirring and shaking.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The surface resistance is determined.

A blank PET substrate yields the following reference values when measured:

Surface resistance: 1.8×10 ¹¹ Ohm/sq

Transmittance: 91%

Dilution of Dispersion 19 and Dispersion 20 with various solvents. Example dispersion menstruum Solubility surface resistance
[Ohm/sq] transmittance
[%] 21A 19 1-methoxy-2-propanol + 1.1×10 ⁷ 89 21B 19 isopropanol + 1.6×10 ⁷ 89 21C 19 toluene + 1.2×10 ⁷ 89 21D 19 butyl acetate + 1.8×10 ⁷ 89 21E 19 Butyl Benzoate + 1.0×10 ⁷ 89 21F 19 1-Methoxy-2-propyl acetate + 1.2×10 ⁷ 89 21G 19 ethyl acetate + 1.4×10 ⁷ 89 21H 19 anisole + 6.7×10 ⁶ 89 21I 20 1-methoxy-2-propanol + 1.7×10 ⁶ 89 21J 20 ethanol + 3.9×10 ⁷ 90 21K 20 butyl acetate + 1.0×10 ⁶ 89 21L 20 anisole + 7.8×10 ⁵ 89

Table 7 shows that the dispersions from Examples 19 and 20 of the present invention show good surface resistance and form stable dispersions in a variety of common organic solvents.

Example 22

A 250 mL 3-necked round bottom flask equipped with a mechanical stirrer was charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid. (9.3 mmol, Aldrich). After heating to 60 °C, 1.565 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.565 g of 3-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (2 mmol; CAS: 210476- 55-4) is added over 40 minutes. The dispersion is stirred at 60° C. for a further 3 h and then cooled to room temperature.

50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol are added to a 100 ml flask and mixed through gentle stirring of the resulting dispersion.

This is called dispersion 22.

Analysis of Dispersion 22:

Solids content: 2.3% (wt)

Sheet resistance (12 μm on PET): 63000 Ohm/sq

Example 23

Dispersion 19 and Dispersion 22 were tested for their compatibility with acrylic resins. Table 8 shows the amount of dispersion, solvent, dipentaerythritol penta-/hexa-acrylate (CAS 60506-81-2, Sigma Aldrich) used.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The surface resistance is determined.

Surface Resistance of Dispersion 19 and Dispersion 22 in Acrylic Resins. Example dispersion menstruum dipentaerythritol penta-/hexa-acrylate [g] surface resistance
[Ohm/sq] 23A 0.6 g dispersion 19 8.4 g 1-methoxy-2-propanol One 6.1×10 ¹⁰ 23B 1.5 g dispersion 19 7.5 g 1-methoxy-2-propanol One 2.5×10 ⁹ 23C 2.4 g dispersion 19 6.6 g 1-methoxy-2-propanol One 6.1×10 ⁷ 23D 0.6 g dispersion 19 8.4 g ethyl acetate One 1.1×10 ¹¹ 23E 1.5 g dispersion 19 7.5 g ethyl acetate One 5.5×10 ⁸ 23F 2.4 g dispersion 19 6.6 g ethyl acetate One 7.7×10 ⁸ 23G 2.4 g dispersion 22 6.6 g ethyl acetate One 7.0×10 ⁷

Table 8 shows the compatibility of dispersions 19 and 22 with acrylic resins as evidenced by the surface resistance values achieved.

Example 24

Dispersion 19 and Dispersion 2B are compared with respect to compatibility with silicone release resins. Table 9 shows the amount of dispersion, solvent, and KS 847-H (CAS: 63148-53-8; Shin-Etsu Silicone) used. As solvent, mixtures of toluene, alkanes and ketones are used.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The surface resistance is determined.

Surface resistivity of Dispersion 19 and Dispersion 24 in silicone release resins. Example dispersion menstruum
[g] KS 847-H
[g] surface resistance
[Ohm/sq] 24A (invention) 0.5 g dispersion 19 10 1.3 1.5×10 ¹¹ 24B (invention) 1 g dispersion 19 10 1.3 1.3×10 ⁹ 24C (invention) 2 g dispersion 19 10 1.3 2.3×10 ⁷ 24E (comparative example) 0.5 g dispersion 2B 10 1.3 2.3×10 ¹¹ 24F (comparative example) 1 g dispersion 2B 10 1.3 2.3×10 ¹¹ 24G (comparative example) 2 g dispersion 2B 10 1.3 2.3×10 ¹¹

Table 9 shows the good compatibility of dispersion 19 with the silicone release resin as evidenced by the surface resistance values achieved.

Example 25

Dispersion 19 and Dispersion 22 were tested for compatibility with polyacrylic resins. Table 10 shows the amount of dispersion, solvent, and polybutylacrylate (CAS 9003-49-0, Sigma Aldrich) used.

Using a wire-bar, a 12 μm wet film was deposited on a PET substrate and dried in an oven at 130° C. for 15 minutes. The surface resistance is determined.

Surface resistance of Dispersion 19 and Dispersion 22 in polyacrylic binders. Example dispersion toluene
[g] polybutyl acrylate
[g] surface resistance
[Ohm/sq] 25A 0.455 g dispersion 19 5.545 4 4.1×10 ¹⁰ 25B 1.136 g dispersion 19 4.864 4 5.3×10 ⁹ 25C 2.273 g dispersion 19 3.727 4 1.7×10 ⁹ 25D 2.273 g dispersion 22 3.727 4 1.7×10 ⁹

Table 10 shows the compatibility of dispersions 19 and 22 with poly(meth)acrylate binders as evidenced by the achieved surface resistivity.

Example 26

A 250 mL 3-necked round bottom flask equipped with a mechanical stirrer was prepared with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 2.981 g of 4-dodecylbenzenesulfonic acid ( 9.3 mmol, Aldrich). After heating to 60° C., 1.584 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT;CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.553 g g (2 mmol) of the product obtained from the reaction in Example 18 are added over 40 minutes. The dispersion is stirred at 60° C. for a further 3 h and then cooled to room temperature.

5 g of the dispersion, 3 g of anisole, and 2 g of n-butanol were mixed via gentle stirring and subjected to 1 min of sonication (Hielscher UP 200 S, cycle 1, amplitude 100%) as a result The resulting dispersion is calculated.

This is called dispersion 26.

Analysis of Dispersion 26:

Solids content: 2.4% (wt)

Sheet resistance (12 μm on PET): 19000 Ohm/sq

100: layer body
101: substrate
102: electrically conductive layer

Claims (22)

i) at least one polythiophene comprising monomer units of formula Ia or Ib,
[Formula Ia] [Formula Ib]

here,
* indicates a bond to a neighboring monomer unit,
X, Z represents O or S,
R ¹ -R ⁶ independently of each other represent a hydrogen atom or an organic residue R,
provided that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ represent the organic residue R;
ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein said organic compound or salt thereof has a molecular weight of less than 1,000 g/mol; and
iii) at least one organic solvent. The method according to claim 1,
wherein the composition is a dispersion, wherein the polythiophene i) and the organic compound ii) form a complex uniformly dispersed in an organic solvent iii). The method according to claim 1 or 2,
wherein the organic moiety R bears no anionic groups. 4. The method according to any one of claims 1 to 3,
The polythiophene is a homopolymer or copolymer comprising a monomer unit of formula Ia, wherein X and Z represent O, and a residue selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ . A composition wherein three of them represent hydrogen atoms and the remaining residues represent an ether group having the formula (IIa):
[Formula IIa]
-(CR ⁷ R ⁸ ) _n -OR ⁹
here,
R ⁷ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group, preferably H;
R ⁸ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group, preferably H;
n is an integer ranging from 0 to 10; and
R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group. 4. The method according to any one of claims 1 to 3,
The polythiophene is a homopolymer or copolymer comprising a monomer unit of formula Ia, wherein X and Z represent O, and a residue selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ . A composition wherein three of them represent a hydrogen atom and the remaining residues represent an alkyl group having the formula (IIb):
[Formula IIb]
-C _n H _2n+1
where n is an integer ranging from 1 to 20. 4. The method according to any one of claims 1 to 3,
The polythiophene is a homopolymer or copolymer comprising a monomer unit of formula Ia, wherein X and Z represent O, and a residue selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ . 3 of which represents a hydrogen atom, and the remaining residues represent a branched alkyl group or a branched ether group. 7. The method of claim 6,
wherein the remaining moieties represent a branched ether group having the formula IIc:
[Formula IIc]
-(CR ¹⁰ R ¹¹ ) _n -OR ¹²
here,
R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group;
R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group;
n is an integer ranging from 0 to 10; and
R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain. 8. The method of claim 7,
R ¹² is an organic moiety having formula IId:
[Formula IId]
-(CHR ¹³ ) _m -R ¹⁴
here,
m is 1, 2 or 3,
R ¹³ is H or a C ₁ -C ₁₂ alkyl group, with the proviso that only one of the structural units -CHR ¹³ -, R ¹³ is a C ₁ -C ₁₂ alkyl group;
R ¹⁴ is a C ₁ -C ₁₀ -alkyl group or an aryl group. 9. The method according to any one of claims 1 to 8,
The composition comprises:
iv) a composition further comprising at least one non-conductive oligomeric or polymeric binder, preferably poly(meth)acrylate and/or polysilicon. 10. The method according to any one of claims 1 to 9,
The organic compound ii) is an anionic surfactant, preferably a monovalent sulfonic acid or a salt thereof. 11. The method according to any one of claims 1 to 10,
Said at least one organic solvent iii) is, toluene, xylene, anisole, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl prop Cypionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2-propylacetate, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or these A composition selected from the group consisting of a mixture of one or two of the aprotic solvents and one or two additional solvents. 12. The method according to any one of claims 1 to 11,
wherein the composition has an iron content of less than 30 ppm, based on the total weight of the composition. I) providing a reaction mixture comprising
i) a thiophene monomer of formula (VIa) or (VIb);
[Formula VIa] [Formula VIb]

here,
X, Z represents O or S,
R ¹ -R ⁶ independently of each other represent a hydrogen atom or an organic residue R,
provided that at least one of the residues R ¹ to R ⁴ and one of the residues R ⁵ and R ⁶ represent the organic residue R;
ii) 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), 1 or 2 sulfuric acid group(s), 1 or 2 phosphonic acid group(s) or 1 or 2 phosphoric acid group(s) at least one organic compound having (s), or a salt of said organic compound, wherein said organic compound or salt thereof has a molecular weight of less than 1,000 g/mol;
iii) at least one organic solvent; and
iv) at least one oxidizing agent, preferably at least one organic peroxide;
II) oxidatively polymerizing the thiophene monomer to form polythiophene. 14. The method of claim 13,
The reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa), wherein X and Z represent O and one of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ 3 represents a hydrogen atom and the remaining residues represent an ether group having the formula (IIa):
[Formula IIa]
-(CR ⁷ R ⁸ ) _n -OR ⁹
here,
R ⁷ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group, preferably H;
R ⁸ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group, preferably H;
n is an integer ranging from 0 to 10; and
R ⁹ is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C ₁ -C ₃₀ alkyl group. 14. The method of claim 13,
The reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa), wherein X and Z represent O and one of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ 3 represents a hydrogen atom and the remaining residues represent an alkyl group having the formula (IIb):
[Formula IIb]
-C _n H _2n+1
where n is an integer ranging from 1 to 20. 14. The method of claim 13,
The reaction mixture provided in process step I) comprises a thiophene monomer of formula (VIa), wherein X and Z represent O and one of the residues selected from the group consisting of R ¹ , R ² , R ³ and R ⁴ 3 represents a hydrogen atom and the remaining residues represent a branched alkyl group or a branched ether group. 17. The method of claim 16,
wherein the remaining moieties represent a branched ether group having the formula IIc:
[Formula IIc]
-(CR ¹⁰ R ¹¹ ) _n -OR ¹²
here,
R ¹⁰ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group;
R ¹¹ is H, a C ₁ -C ₁₀ -alkyl group or a C ₁ -C ₁₀ -alkoxy group;
n is an integer ranging from 0 to 10; and
R ¹² is a branched organic moiety, preferably a branched alkyl group or branched arylalkyl group, more preferably a branched alkyl group or branched arylalkyl group having no unsaturated C=C-bond in the alkyl chain. 18. The method of claim 17,
R ¹² is an organic moiety having the formula IId:
[Formula IId]
-(CHR ¹³ ) _m -R ¹⁴
here,
m is 1, 2 or 3,
R ¹³ is H or a C ₁ -C ₁₂ alkyl group, with the proviso that only one of the structural units -CHR ¹³ -, R ¹³ is a C ₁ -C ₁₂ alkyl group;
R ¹⁴ is a C ₁ -C ₁₀ -alkyl group or an aryl group. A layer structure (100) comprising a substrate (101) and an electrically conductive layer (102) applied on the substrate (101), wherein the electrically conductive layer (102) comprises: polythiophene i) as defined in and 1 or 2 inorganic acid group(s), preferably 1 or 2 sulfonic acid group(s), as defined in claims 1, 3 and 10, 1 or 2 at least one organic compound ii) bearing two sulfuric acid group(s), one or two phosphonic acid group(s) or one or two phosphoric acid group(s), or a salt of said organic compound. ). A) providing a substrate 101;
B) coating the substrate (101) with a composition according to any one of claims 1 to 12 or a composition obtainable by a method according to any one of claims 13 to 18; and
C) at least partially removing the organic solvent iii) to form an electrically conductive layer (102). An electronic component comprising a layer structure 100 according to claim 19 or a layer structure obtainable by the method according to claim 20 . The composition of any one of claims 1 to 12 or the composition obtainable by the method according to any one of claims 13 to 18 for producing an electrically conductive layer or for producing an antistatic coating on an electronic component. How to use.

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